JP2001323069A - Gel-like composition, ion conductive composition comprising the same as base and electric cell using thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a gel-like composition and an ion conductive composition comprising the same as a base and provide an electric cell using thereof. SOLUTION: This gel-like composition comprises a polymer obtained by reacting a linear copolymer of a compound expressed by formula (A) and a compound expressed by formula (B) and having two hydroxyl groups with a compound expressed by formula (D) having >=3 alkenyl groups and a solvent. This ion conductive composition comprises the same composition as a base and this electric cell is produced by using the ion conductive composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gel composition, an ion-conductive composition based on the composition, and a battery using the composition. More specifically, the present invention relates to a gel composition containing a block polymer, an ion conductive composition based on the same, and a battery using the same.

[0002]

2. Description of the Related Art Ion conductive materials are used in various batteries and devices such as primary batteries, secondary batteries, solar batteries, electrolytic capacitors, sensors, and electrochromic display devices. In recent years, in the electronics industry, various electronic components have been further pursued with higher performance, and their miniaturization and thinning have been increasingly advanced. There is a need for improvements in line with this. In addition, ion conductive materials conventionally used in the form of a liquid or a fluid have problems such as damage to a peripheral portion due to liquid leakage.

In order to address such problems, recently, solid electrolyte materials such as polymer electrolytes and gel electrolytes have been proposed. These include relatively high ionic conductivity, wide potential window, good thin film formation, flexibility, light weight,
It has excellent characteristics such as elasticity and transparency. Among these, properties such as flexibility and elasticity unique to polymer electrolytes are:
This is particularly important in a lithium secondary battery in which many electrode active materials change their volume during operation, because the volume change can be absorbed. In addition, polymer electrolytes and gel electrolytes include:
It is said that it also has the ability to prevent a decrease in battery capacity and a short circuit between the positive and negative electrode materials during repeated use due to detachment of the electrode material.

Japanese Patent Publication No. 239394/1986 mentions a one-dimensional polyamide resin as an organic polymer compound for use in such a polymer electrolyte. No base resin is disclosed. Also, Advanced Materials, 10, 439 (1998)
Include polyoxyethylene; a composite of polyoxyethylene and polysiloxane; a composite of polyoxyethylene and polyphosphazene; having a polyoxyethylene as a structural unit and having an epoxy group, an isocyanate group, and a siloxane structure. And a crosslinked polymer having the formula: In particular, a polymer having a crosslinked structure having a polyoxyalkylene group and a polysiloxane structure is a polymer electrolyte that attracts attention because of its excellent low-temperature properties. As such a polymer for a polymer electrolyte having a polyoxyalkylene group and a polysiloxane structural unit, J. Poly
m. Sci. Polym. Lett. Ed., 22, 659 (1984)

[0005]

Embedded image Is disclosed. Also, Solid State Ionics, 15, 23
3 (1985)

[0006]

Embedded image And JP-A-63-136409 discloses that

[0007]

Embedded image And JP-A-8-78053 discloses that
formula:

[0008]

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A silicone compound represented by the formula:
Disclosed are compounds wherein A and A 'are alkyl groups and B and / or B' are oxyalkylene chains. Each of these polymers has only a polyoxyalkylene chain on the side chain of the polysiloxane main chain. Tokuhei 8-
JP-A-21389 discloses a cross-linked cured polysiloxane having an organic group having an oxyalkylene group or a polyoxyalkylene group as a side chain and / or as a cross-linking portion.

[0010]

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A crosslinked cured polysiloxane represented by the formula:
What, R¹, R^Two, R^Three, R¹¹And R ^{11 '}Is alkyl
Group, an alkoxyl group or an aryl group,^FourIs al
Kylene group, oxyalkylene group or oxycarbonyl group
A alkylene group;^FiveIs a hydrogen atom or an alkyl group
Wherein Y is an oxyalkylene group or a polyoxyalkylene
Z is an oxyalkylene group at both ends, a polyoxy group.
A silalkylene group or a group having a polysiloxane structure
Cured products are disclosed. However, these yes
The gap may cause problems with the stability of the polymer itself,
A crosslinked structure that suppresses material detachment and enables thinning
It is not possible to obtain sufficient ion conductivity
There are some problems and they have not yet been put to practical use.

[0012]

An object of the present invention is to provide a gel composition, an ion-conductive composition based on the composition, and a battery using the composition.

[0013]

According to the present invention, there is provided a compound of formula (A):

[0014]

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[Wherein, R ^{1 s} independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, R ² , independently of one another, have 1 to 18 carbon atoms
Alkylene group, substituted or unsubstituted C6-20
, An arylalkylene group having 7 to 21 carbon atoms, a dialkyl (poly) silylene group, a diaryl (poly) silylene group, or a direct bond, and Z ¹ is
It represents a divalent group derived from polyoxyalkylene, (poly) carbonate, (poly) ester, polyacrylate, polymethacrylate, alkylene, or a direct bond. [Hereinafter referred to as compound (A)] and a compound represented by formula (B):

[0016]

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Wherein R ³ is independently a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms,
Aralkyl group to 21, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, n ¹ is an integer of 0 to 500. [C] a linear copolymer obtained by an addition reaction with a compound represented by the following formula [hereinafter referred to as compound (B)], having two terminal hydrosilyl groups:

[0018]

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Wherein R ¹ , R ² , R ³ , Z ¹ , and each n ¹ are as defined above, and p is an integer from 1 to 100. The compound (A) and / or the copolymer [hereinafter referred to as a linear copolymer (C)]
Or a compound of the formula (D) having three or more alkenyl groups in the presence or absence of the compound (B):

[0020]

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Wherein R ⁴ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; R ⁵ are independently of one another,
Represents a divalent group derived from a heteroatom-containing alkylene group having 13 to 100 carbon atoms, a (poly) carbonate, a (poly) ester, a polyacrylate or a polymethacrylate, wherein n ² is an integer of 3 or more. Yes, and
Z ² is a linking group having the same valence as n ² and includes a carbon atom, a silicon atom, a monosubstituted trivalent silicon atom, and a carbon atom having 1 to 3 carbon atoms.
0 aliphatic group, heteroatom-containing organic group having 1 to 6 carbon atoms and 1 to 30 hetero atoms, benzene polycarboxy group, phosphoric acid group, linear, branched or cyclic having 2 to 50 silicon atoms Represents an alkylpolysiloxane group or an alkylarylpolysiloxane group. A gel comprising a linear copolymer (C) as a basic unit and a solvent, which is obtained by an addition reaction of a compound [hereinafter referred to as compound (D)] A composition is provided.

In another aspect, the present invention provides a compound (A)
Provided is a gel composition comprising a polymer and a solvent obtained by simultaneously subjecting compound (B) and compound (D) to an addition reaction. In still another aspect, the present invention also provides a gel composition comprising a polymer obtained by subjecting compound (B) to addition reaction with compound (D) and a solvent. The present invention also provides an ion conductive composition based on the gel composition. The present invention further provides a battery comprising the ion-conductive composition.

In the formula (A), R¹ A shown by
Examples of the alkyl group include a methyl group, an ethyl group, and a propyl
Group, butyl group, octyl group, dodecyl group, etc.
And the aryl group includes, for example, phenyl group, toluyl
Group, naphthyl group and the like. R^Two Al indicated by
For example, a methylene group, an ethylene group,
Pyrene, butylene, octylene, dodecylene, etc.
And the arylene group includes, for example, phenylene,
Including a ruylene group, a naphthylene group, etc .;
Examples of the alkylene group include a phenylmethylene group,
Phenylethylene group, phenylethylidene group, etc.
You. Z¹The alkylene group represented by^Two About
It is the same as that shown. Preferably, R¹ Is hydrogen field
Or a methyl group;^Two Is an alkylene having 1 to 4 carbon atoms
Or a direct bond, and Z¹Is an alkylene or
Is a polyoxyalkylene, (poly) carbonate,
(Poly) ester, polyacrylate, polymethacrylate
A divalent chain derived from a salt or polysiloxane
is there. More preferably, R¹ Is a hydrogen atom, and R^Two Is
A methylene group or a direct bond, and Z¹Is a poly
An oxyalkylene chain or (poly) carbonate
Chains or (poly) ester chains,
And most preferably, Z¹Is
It is a lioxyalkylene chain. Polyoxyalkylene chain
Has a poly (oxymethylene) chain and a poly (oxyethylene)
Chain, poly (oxypropylene) chain, poly (oxy
(Tylene) chains, poly (oxypentylene) chains, and the like
Is included. Such polyoxyalkylene
Chain, (poly) carbonate chain or (poly) ester chain
Is from 60 to 30,000, preferably from 100 to 5,000
It has a molecular weight of 0.

[0024] With the terminal alkenyl group in these compounds
Z¹Bond with Z¹Is determined by the type of chain. An example
For example, Z¹Is a polyoxyalkylene chain;
The alkenyl group is linked by an ether bond, Z¹But polyeste
In the case of an alkyl chain, the terminal alkenyl group is an ether bond or an ether bond.
They are linked by steal bonds.

In the formula (B), the alkyl group represented by R ³ includes, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a dodecyl group, and the like. A benzyl group, a phenethyl group and the like are included, and an aryl group includes, for example, a phenyl group, a toluyl group, a naphthyl group and the like. The substituted alkyl group represented by R ³ includes, for example, a halogenated alkyl group such as a trifluoropropyl group and a chloropropyl group, and a cyanoalkyl group such as a 2-cyanoethyl group. Preferably, R ³ is a methyl group and n ¹
Is an integer of 1 to 50.

The compound (A) and the compound (B) are alternately subjected to an addition reaction to form a linear copolymer (C). In particular, when both the compound (A) and the compound (B) are polymers, a linear block copolymer is formed. When reacting these two compounds, compound (B) is added in excess to have two hydrosilyl groups at the terminals.
For example, when 1 mol of the compound (A) and 2 mol of the compound (B) are reacted, 1 mol of a linear copolymer (C) having an average structure of BAB is produced. Further, 2 mol of compound (A),
When 3 mol of the compound (B) is reacted, 1 mol of a linear copolymer (C) having an average structure of BABAB is produced. When 3 mol of the compound (A) and 4 mol of the compound (B) are reacted, a linear copolymer (C) having an average structure of BABABAB is obtained.
1 mole is formed. Specific examples of the compound (A) include:

[0027]

Embedded image Polyoxyalkylenes having alkenyl groups at both terminals, such as;

[0028]

Embedded image Polycarbonates having alkenyl groups at both terminals, such as;

[0029]

Embedded image Polyesters having alkenyl groups at both terminals, such as;

[0030]

Embedded image Alkylene having an alkenyl group at both terminals, such as;

[0031]

Embedded image Polyacrylates having alkenyl groups at both terminals, such as;

Embedded image

And polymethacrylates having alkenyl groups at both ends. Specific examples of the polysiloxane compound represented by the formula (B) include:

[0033]

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And the like. When these specific compounds (A) and (B) are reacted, a linear polysiloxane block copolymer in which they are alternately arranged is formed.

The addition reaction (hydrosilylation reaction) between the compound (A) and the compound (B) has a large temperature dependence on the reaction rate. it can. This is a great advantage of the hydrosilylation reaction. If the reactants are mixed with an appropriate viscosity, molded and then heated, a polymer having a desired shape can be obtained at once. The heating temperature in this case is from room temperature to about 150 ° C., preferably from about 40 ° C. to about 120 ° C. A catalyst is used in this hydrosilylation reaction. As the catalyst, compounds such as platinum, ruthenium, rhodium, palladium, osmium, and iridium are known. But,
For batteries, it is necessary to have conditions such as high activity for rapid reaction progress, no secondary reaction with reaction products, and no effect on battery characteristics. Useful. Examples of platinum compounds include:
Chloroplatinic acid, simple substance of platinum, alumina, silica, carbon black, etc., with solid platinum supported on
Vinylsiloxane complex, platinum-phosphine complex, platinum-
A phosphite complex, a platinum alcoholate catalyst or the like can be used. In the hydrosilylation reaction, a platinum catalyst is added in an amount of about 0.0001 to 0.1% by weight as platinum.
The molecular weight of the obtained linear copolymer (C) is 1,000 or more, preferably 3,000 to 100,000.

In the formula (D), the alkyl group represented by R ⁴ includes, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a dodecyl group, and the like. For example, a phenyl group, a toluyl group, a naphthyl group and the like are included. The term R is used for ⁵ "hetero atom-containing alkylene group", as a hetero atom, an oxygen, a group containing a sulfur or nitrogen atom, by to them heteroatom regarded as carbon atoms, the total It means a group that can be regarded as an alkylene group. Such groups include poly (oxymethylene) groups,
Poly (oxyethylene) group, poly (oxypropylene)
Groups, poly (oxybutylene) groups, poly (oxypentylene) groups, and their copolymers, those in which oxygen atoms have been replaced by sulfur or nitrogen atoms, and some of these oxygen atoms have sulfur and And / or nitrogen atoms. Such groups have a lower limit of any one of these heteroatoms having 1 and 13 carbon atoms,
Having 50 heteroatoms and 400 carbon atoms, preferably 1
It has a molecular weight whose upper limit is 00. The monosubstituted trivalent silicon atom represented by Z ² includes, for example, a compound of the formula
Alkyl include, it can be exemplified · Si-CH ₃ specific examples. The aliphatic group represented by Z ² includes
It includes a tri- or higher valent linear or branched alkyl group, and includes, for example, a methynyl group, an ethynyl group, a propynyl group, a butynyl group, an octynyl group, a dodecynyl group and the like. Z ²
The term "heteroatom-containing organic group" as used for refers to an aliphatic or aromatic group containing, as a heteroatom, an oxygen, sulfur or nitrogen atom. Such groups include methyleneoxymethynyl, methyleneoxyethynyl, methyleneoxypropynyl, ethyleneoxypropynyl, methyleneoxyethyleneoxymethynyl, emethyleneoxyethyleneoxyethynyl, propyleneoxyethyleneoxypropynyl Phenylenebis (methyloxyethynyl) groups, those in which oxygen atoms have been replaced by sulfur or nitrogen atoms, and those in which some of these oxygen atoms have been replaced by sulfur and / or nitrogen atoms. The alkyl group of the alkylpolysiloxane group and the alkylarylpolysiloxane group represented by Z ² includes an alkyl group having 1 to 18 carbon atoms, and the aryl group includes an aryl group having 6 to 20 carbon atoms. Specific examples of these groups include those mentioned for R ^{1 in} formula (A). Preferably, R ⁴ is a hydrogen atom or methyl, and R ⁵ is —CH ₂ OCH ₂ —, —CH
₂ OCH ₂ CH ₂ — or —CH ₂ OCH ₂ CH ₂ OC
H ₂ —. Specific compounds (D) include the following.

[0037]

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[0038]

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[0039]

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This polymer is a polymer having a linear copolymer (C) as a basic unit and capable of forming a network structure through a compound having three or more alkenyls. Become. Further, when an electrolyte is contained, the composition becomes a gel-like ion conductive composition. The crosslink density of the crosslinked copolymer of the present invention is determined to some extent by the molecular weight of the linear copolymer (C), and the linear copolymer (C) and the compound (D) have the formula:

[0041]

0.5 ≦ [(mol of D × valence of D) / (mol of C × 2)] ≦ 1.5 (I)

In particular, when the lower limit of the formula (I) is set to 0.
When the upper limit is 1.2 and the upper limit is 1.2, a copolymer having a preferable crosslinking density is obtained. Compound (A), compound (B),
When the crosslinked copolymer of the present invention is obtained without reacting via the linear copolymer (C) by reacting the compound (D) and the compound (D) at once, those compounds are represented by the formula:

[0043]

0.4 ≦ [mol number of A / mol number of B] ≦ 1.2 (II) and

[0044]

0.05 ≦ [(mol of D × valence of D) / (mol of B × 2)] ≦ 1.0 (III)

It is particularly preferable that the lower limit of formula (II) is 0.6 and the upper limit is 1.0, and the lower limit of formula (III) is 0.1 and the upper limit is 0.6. A copolymer having a crosslink density is obtained. The compound (A), the compound (B), and the compound (D) may each be used in combination of two or more. When reacting the compound (D) with the linear copolymer (C), the compound (A) and / or the compound (B) may be added.

Solvents present in the obtained crosslinked copolymer include water, inorganic solvents such as thionyl chloride, sulfuryl chloride and liquid ammonia, sulfur compounds such as thiophene and diethyl sulfide, and nitrogen compounds such as acetonitrile, diethylamine and aniline. Compounds, fatty acids such as acetic acid and butyric acid, and acid anhydrides thereof, ketones such as ether, acetal and cyclohexanone, esters, phenols, alcohols, hydrocarbons, halogenated hydrocarbons, dimethylpolysiloxane and the like can be used. In particular, for lithium secondary batteries, purified dimethyl sulfoxide, sulfur compounds such as sulfolane, propylene carbonate, ethylene carbonate,
ester compounds having a carbonyl bond such as γ-butyrolactone, dimethyl carbonate, diethyl carbonate, etc., tetrahydrofuran, 2-methoxytetrahydrofuran, 1,3-dioxolan, 1,2-dimethoxyethane, 1,2-ethoxyethane, 1,3- Ether compounds such as dioxane can be used alone or in combination. These solvents are present in the gel composition of the present invention in an amount of 1 to 99% by weight, preferably 50 to 99% by weight, more preferably 80 to 97% by weight. Among these solvents, those that do not inhibit the hydrosilylation reaction are preferably added during the production of the gel composition. In addition, as a solvent that inhibits the hydrosilylation reaction, water, alcohol, and the like can be given.

[0047] Gel composition to gel ion conductive composition
When used as a component of
To keep good, the amount of solvent is 50-95% by weight
Is preferred. At this time, the storage elastic modulus of the gel electrolyte is 300
0 pascal or more is preferable, especially 5000 pascal or more
Is preferred. The storage modulus indicates the mechanical behavior of the gel
Although this is a quantity, of course, this frequency characteristic does not change greatly,
Those exhibiting good shape stability characteristics are more preferable.

The gel ion-conductive composition of the present invention is obtained by mixing an electrolyte with the above-mentioned polymer and, if necessary, mixing a modified silicone and other components conventionally blended with the ion-conductive composition. Alternatively, it is produced by impregnation. Further, all or a part of these components may be blended with the polymerization reactant before the polymer is obtained, and the remainder may be blended after the polymerization reaction. For example, a linear copolymer (C) and a compound (D)
May be blended before or after the reaction. In addition, it is also possible to blend a part before blending and then blend the rest. In the ion conductive composition of the present invention, the polymer of the present invention is present in an amount of 1 to 99% by weight, preferably 2 to 49% by weight.

Modified silicone means that a part of the methyl group of dimethylpolysiloxane is a polyether group, polyester group, alkoxy group, alcohol group, carboxy group, epoxy group-containing group, amino group-containing group, alkyl group, phenyl group and the like. Say the replacement. The modifying group is pendant,
It is added in the form of linear, one-terminal modification, both-terminal modification, both-terminal and side-chain modification. Further, it may have two or more substituents. Their viscosity at 40 ° C. is 10,000 cP or less, preferably 2000 cP or less, more preferably 1000 cP or less. These modified silicones are mixed in the ion conductive composition of the present invention in an amount of 0.01 to 50% by weight, preferably 0.1 to 10% by weight. The modified silicone used is, in particular, a pendant-modified polyether-modified silicone (X) represented by the following formula:

[0050]

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Wherein R is independently of each other
And R ′ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, and a butyl group). And n ² represents an integer of 1 to 30,
n ³ represents an integer of 0 to 20, a is an integer of 1 to 20, and b is an integer of up to 0-20. Is preferred. In particular,

[0052]

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And the like. Compound (X-
The viscosity of 1) was 173 cP at 40 ° C. as measured with a B-type viscometer (rotor number 2, rotation speed 60 rpm, manufactured by Tokyo Keiki Co., Ltd.) which is a rotational viscometer. Examples of the electrolyte for constituting the ion conductive composition include various fluorides such as lithium fluoride, sodium fluoride, potassium fluoride and calcium fluoride, various chlorides such as lithium chloride, sodium chloride and calcium chloride, and metals. Bromide, metal iodide, metal perchloride, metal hypochlorite, metal acetate, metal formate, metal permanganate, metal phosphate, metal sulfate, metal nitrate, metal thiosulfate, metal thiocyanate Salts, and further include ammonium salts such as ammonium sulfate and tetra-n-butylammonium perchlorate. Further, in lithium batteries and the like, LiAlCl ₄ ,
LiClO ₄ , LiBF ₄ , LiPF ₆ , LiAs
F ₆ , LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ ,
LiC (CF ₃ SO ₂ ) ₃ and / or LiBPh
₄ (where Ph represents a phenyl group) and the like can be used. These electrolytes are contained in the ion conductive composition of the present invention in an amount of 0.1 to 60% by weight, preferably 1.0 to 4% by weight.
It is present at 0% by weight.

Further, a polyalkylene oxide compound such as tetraethylene glycol dimethyl ether and tetrapropylene glycol dimethyl ether, a modified polyacrylate having a polyalkylene oxide as a structural unit,
An ion conductive polymer such as modified polyphosphazene having a structural unit of polyacrylonitrile, polyvinylidene fluoride, or polyalkylene oxide can also be blended.

It is desirable that the obtained gel ion-conductive composition has excellent shape stability and ionic conductivity and does not leak, and therefore has a high storage modulus which is an index of gel strength. . The storage modulus is an amount that indicates the mechanical behavior of a gel.When a dynamic gel with a different frequency is applied to a gel of a certain size, the displacement (strain, strain) corresponding to the width of the frequency is applied. ) Or by measuring the dynamic stress that results in a constant displacement width. Displacement can be measured, for example, by Rheometrics RSA-II, and dynamic stress can be measured, for example, by Perkin Elmer DMA-7. The higher the storage modulus, the harder the gel. For example, 10 water ^-2, the polystyrene 10 ^10, and the tungsten is 10 ¹² the order of.

In order to operate as a battery, it is said that ionic conductivity is required to be about 10 ⁻³ S / cm at room temperature, and an ionic conductivity of 50% or more of the ionic conductivity of the electrolytic solution itself is required. It is preferable to hold. In particular, if the ionic conductivity decreases at a low temperature of about −20 ° C., the use environment is restricted, which is not preferable. Without wishing to be bound by theory, the polymers of the present invention have a more uniform dispersion and retention of the electrolyte or both the electrolyte and the solvent than conventional ones due to a more ordered and uniform molecular structure than conventional polymers. It is considered possible to provide a composition having good shape stability and ionic conductivity.

As a method for manufacturing a battery using the above-mentioned ion conductive composition, a method of preparing an outer shell of the battery in advance and then performing a heating reaction in the outer shell to obtain an ion conductive composition, There are various methods such as a method of assembling a battery after obtaining a conductive composition. Further, in order to further improve the shape retention and shutdown effect of the ion conductive composition, a porous film produced from a thermoplastic resin,
Non-woven fabric or thermoplastic resin particles may be used in combination. When a porous film or nonwoven fabric of a thermoplastic resin is used, the film or nonwoven fabric is impregnated with the ion conductive composition of the present invention.

The porous film produced from a thermoplastic resin is, for example, a film obtained by making a film of polyethylene, polypropylene or the like porous by uniaxial stretching or the like. A weight of about 5 g / m ² to 30 g / m ² is used. As a nonwoven fabric sheet made from a thermoplastic resin, firstly, a polymer or gel electrolyte produced has a low resistance to ionic conductivity, and has excellent electrolyte retention. Can be used. As the method for producing the nonwoven fabric, either a wet method or a dry method can be used, and the basis weight is 100 g / m ² or less, preferably 5 to 50 g / m ² . Examples of the fiber material used include polyester, polypropylene, polyethylene, and Teflon (registered trademark), but are not particularly limited thereto.

The thermoplastic resin particles include polyethylene,
It is a fine particle of a material such as polypropylene or Teflon, and has a diameter of 20 μm or less, preferably 10 μm or less. Such fine particles are synthesized by emulsion polymerization or produced by pulverization. Particle mixing ratio is 5%
To about 50%. Also, when particles are present in the gel, after being deformed to a certain shape by hot pressure,
It can also be used as an ion conductive composition.

In a lithium primary battery, metallic lithium is used as a negative electrode, and as a positive electrode, graphite fluoride, γ-β type manganese dioxide, sulfur dioxide, thionyl chloride, iodine / poly (2-vinylpyridine), Ag ₂ CrO ₄ , Vanadium pentoxide, CuO, MoO ₃ or the like can be used.
The ion conductive composition of the present invention is used as a substitute for the electrolyte of the primary battery. As the shape of the battery, a coin type, a cylindrical type, and a sheet (paper) type are used.

In the lithium secondary battery, the positive electrode materials used are LiCoO ₂ , LiNiO ₂ , spinel type LiMn ₂ O ₄ , amorphous V ₂ O ₅ , β-MnO 2.
₂ and Li ₂ MnO ₃ mixture, spinel superlattice structure L
i _4/3 Mn _5/3 O ₄ , 2,5-dimercapto-3,4-
An organic disulfide compound such as thiadiazole or the like is used as a positive electrode active material, this is powdered, and a conductive agent such as acetylene black and a thickener made of an organic polymer compound are added to form a positive electrode material. The positive electrode material is applied on aluminum, which is a positive electrode current collector, and is used as a porous material.

The negative electrode material is metallic lithium, lithium-aluminum alloy, Li-Pb-Cd-In alloy, lithium-graphite compound, lithium-graphitizable carbon compound, lithium-amorphous tin composite oxide, amorphous Negative electrode active material, such as lithium cobalt-substituted lithium nitride, is plated on a nickel plate or the like when they are metal, and in other cases, powdered like a positive electrode material, using a conductive agent such as acetylene black, or an organic polymer. It is prepared by adding a thickener.
In the case of a paste like the latter, it is applied on a current collector plate such as copper and becomes porous. The ion conductive composition of the present invention is used as a substitute for an electrolyte for a secondary battery. The secondary battery is used in the form of a coin, a cylinder, or a sheet, like the primary battery. Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

[0063]

EXAMPLES Example 1 The following materials were mixed as follows. Compound (B-1) 1.186 g Compound (D-2) 2.814 g 0.25% Pt catalyst 0.60 g LiPF ₆ 7.0 g Ethylene carbonate 12.68 g Diethyl carbonate 25.74 g This mixture was heated at 50 ° C. for 30 minutes to obtain a gelled ion conductive composition 1. This gel ion conductive composition 1
Had an ion conductivity of 2.2 × 10 ⁻³ S / cm.

Example 2 The following materials were mixed as follows. Compound (B-1) 1.073 g Compound (D-1) 2.927 g 0.25% Pt catalyst 0.60 g LiN (CF ₃ SO ₂ ) ₂ 8.2 g Ethylene carbonate 12.26 g Diethyl carbonate 24.90 g Spread on a flat surface and heat at 50 ° C for 30 minutes,
A gel ion conductive composition 2 having a thickness of 40 μm was obtained. The ion conductivity of this gelled ion conductive composition 2 is 2.0
× 10 ^-3 S / cm. On the other hand, the positive electrode layer and the negative electrode layer were taken out from a commercially available lithium secondary battery, and a metal secondary electrode, a positive electrode layer, a gel ion conductive composition 2, a negative electrode layer, and metal copper were laminated to prepare a lithium secondary battery. When the battery was charged and discharged at a current value of 0.1 mA, the capacity was 1.5 mAh / cm ² .

Example 3 The following materials were mixed, reacted at 80 ° C. in a nitrogen atmosphere, and then toluene was removed to obtain a linear block copolymer (C-1) having hydrosilyl groups at both ends. Was synthesized. Compound (A-2) 593.9 g Compound (B-1) 406.1 g toluene 1000g 0.25% Pt catalyst 4.00 g The block polymer (C-1) and each compound were mixed as follows. Block polymer (C-1) 0.838 g Compound (D-2) 0.162g 0.25% Pt catalyst 0.32g LiPF ₆ 2.89 g ethylene carbonate 5.21 g propylene carbonate 10.78 g This was developed into a plane at a basis weight of 15 g / m ² ,
For 30 minutes to obtain a gel-like ion conductive composition 3 having a thickness of 40 μm. The storage elastic modulus of the gel ion conductive composition 3 is 3.0 × 10 ³ Pa, and the ion conductivity is 5.0.
It was 0 × 10 ⁻³ S / cm. On the other hand, commercially available lithium 2
The positive electrode layer and the negative electrode layer were taken out from the secondary battery, and a metallic secondary battery, a positive electrode layer, a gel ion conductive composition 3, a negative electrode layer, and metallic copper were laminated to prepare a lithium secondary battery. When the battery was charged and discharged at a current value of 0.2 mA, the capacity was 1.7 mAh / cm ² .

[0066]Example 4 The following materials are mixed and reacted at 80 ° C. under a nitrogen atmosphere.
After removing toluene, hydrosilyl
To synthesize a linear block copolymer (C-2) having
Was. Compound (A-3) 702.3 g Compound (B-2) 297.7 g toluene 1000g 0.25% Pt catalyst  4.00 g The block polymer (C-2) and each compound were mixed as follows. Block polymer (C-2) 0.918 g Compound (D-1) 0.282g 0.25% Pt catalyst 0.32g LiN (CF_ThreeSO_Two)_Two 3.37 g ethylene carbonate 4.99 g diethyl carbonate 10.12 g This was gelled in a 2 mm thick closed container.
A gel-like ion conductive composition 4 was obtained. This gel-like io
The storage elastic modulus of the conductive composition 4 is 4.0 × 10 ^ThreePa,
The ionic conductivity is 4.0 × 10^-3S / cm.

[0067]Example 5 The following materials are mixed and reacted at 80 ° C. under a nitrogen atmosphere.
After removing toluene, hydrosilyl
To synthesize a linear block copolymer (C-3) having
Was. Compound (A-1) 679.0 g Compound (B-2) 321.0 g toluene 1000g 0.25% Pt catalyst  4.00 g The above block polymer (C-3) and each compound were mixed as follows. Block polymer (C-3) 0.919 g Compound (D-3) 0.081g 0.25% Pt catalyst 0.32g LiPF₆  2.88 g ethylene carbonate 5.31 g diethyl carbonate 10.79 g This was gelled in a 2 mm thick closed container.
A gel-like ion conductive composition 5 was obtained. This gel-like io
The storage elastic modulus of the conductive composition 5 is 4.0 × 10 ^ThreePa,
The ionic conductivity is 5.0 × 10^-3S / cm. one
On the other hand, take the positive electrode layer and the negative electrode layer from a commercially available lithium secondary battery.
Out, metal aluminum, positive electrode layer, gel ion conductivity
Composition 5, negative electrode layer and metallic copper are laminated to form a lithium secondary battery.
A pond was made. Charge and discharge this battery at a current value of 0.1 mA
Was carried out, the capacity was 1.4 mAh / cm^TwoIn
Was.

Example 6 The following materials were mixed as follows. Compound (B-1) 1.483 g Compound (D-2) 3.517 g 0.25% Pt catalyst 0.60 g Ethylene carbonate 6.0 g Diethyl carbonate 12.18 g This mixture was heated at 50 ° C. for 30 minutes to form a gel. Composition 1
I got Next, the following compounds were added to the gel composition 1 to swell, thereby obtaining a gel ion conductive composition 6. LiN (CF ₃ SO ₂ ) ₂ 7.0 g ethylene carbonate 6.0 g diethyl carbonate 12.18 g The ion conductivity of the gelled ion conductive composition 6 is 1.
It was 0 × 10 ⁻³ S / cm.

Example 7 The following materials were mixed, reacted at 80 ° C. under a nitrogen atmosphere, and toluene was removed to obtain a linear block copolymer having hydrosilyl groups at both ends (C-4). Was synthesized. Compound (A-1) 687.8 g Compound (B-2) 312.2 g toluene 1000g 0.25% Pt catalyst 4.00 g The block polymer (C-4) and each compound were mixed as follows. Block polymer (C-4) 1.646 g Compound (D-1) 0.354g 0.25% Pt catalyst 0.32g Ethylene carbonate 2.0 g diethyl carbonate 3.0 g This was gelled in a closed container having a thickness of 2 mm to obtain a gel composition 2. Next, the following compounds were added to swell to obtain a gel-like ion conductive composition 7. LiPF ₆ 2.73 g Ethylene carbonate 2.93 g Diethyl carbonate 7.01 g The storage elastic modulus of this gelled ion conductive composition 7 is 2.0.
× 10 ³ Pa, ionic conductivity 1.0 × 10 ⁻³ S / cm
Met. On the other hand, a positive electrode layer and a negative electrode layer were taken out from a commercially available lithium secondary battery, and a metal secondary layer, a positive electrode layer, a gel ion conductive composition 7, a negative electrode layer, and metallic copper were laminated to prepare a lithium secondary battery. When the battery was charged and discharged at a current value of 0.2 mA, the capacity was 1.3 mAh.
/ Cm ² .

Example 8 The following materials were mixed and reacted at 80 ° C. in a nitrogen atmosphere, and then toluene was removed to obtain a linear block copolymer having hydrosilyl groups at both ends (C-5). Was synthesized. Compound (A-4) 756.8 g Compound (B-1) 243.2 g toluene 1000g 0.25% Pt catalyst 4.00 g The above block polymer (C-5) and each compound were mixed as follows. Block polymer (C-5) 1.677 g Compound (D-2) 0.323g 0.25% Pt catalyst 0.32g ethylene carbonate 1.0g diethyl carbonate 4.0 g of this was gelled in a closed container having a thickness of 2 mm to obtain a gel composition 3. Next, the following compounds were added and swelled to obtain a gel ion conductive composition 8. LiN (CF ₃ SO ₂ ) ₂ 3.22 g Ethylene carbonate 3.77 g Diethyl carbonate 5.68 g The ion conductivity of this gelled ion-conductive composition 8 is 0.
It was 8 × 10 ⁻³ S / cm.

Example 9 The following materials were mixed, reacted at 80 ° C. in a nitrogen atmosphere, and then toluene was removed to obtain a linear block copolymer having hydrosilyl groups at both ends (C-6). Was synthesized. Compound (A-2) 549.3 g Compound (B-1) 450.7 g toluene 1000g 0.25% Pt catalyst 4.00 g The above block polymer (C-6) and each compound were mixed as follows. Block polymer (C-6) 1.475 g compound (D-2) 0.525g 0.25% Pt catalyst 0.32g ethylene carbonate 2.0 g diethyl carbonate 3.0 g of this was gelled in a closed container having a thickness of 2 mm to obtain a gel composition 4. Next, the following compounds were added to swell to obtain a gel-like ion conductive composition 9. LiPF ₆ 2.73 g Ethylene carbonate 2.93 g Diethyl carbonate 7.01 g The ion conductivity of this gelled ion conductive composition 9 is 0.03 g.
It was 9 × 10 ⁻³ S / cm. On the other hand, commercially available lithium 2
The positive electrode layer and the negative electrode layer were taken out from the secondary battery, and a metallic secondary battery, a positive electrode layer, a gel ion conductive composition 9, a negative electrode layer, and metallic copper were laminated to produce a lithium secondary battery. When the battery was charged and discharged with a current value of 0.2 mA, the capacity was 1.1 mAh / cm ² .

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08J 5/04 CFH C08J 5/04 CFH 5H029 C08L 83/04 C08L 83/04 83/10 83/10 83 / 12 83/12 83/14 83/14 101/00 101/00 H01B 1/06 H01B 1/06 A H01M 6/18 H01M 6/18 E 6/22 6/22 C 10/40 10/40 B (72 Inventor Koshiro Ikegami 3-4-2, Marunouchi, Chiyoda-ku, Tokyo, Japan (72) Inventor Kenji Hyoto 3-4-2, Marunouchi, Chiyoda-ku, Tokyo, Japan (72) Inventor Hiroaki Watanabe 3-4-2, Marunouchi, Chiyoda-ku, Tokyo Mitsubishi Paper Mills Co., Ltd. (72) Inventor Kenichi Hino 4-173-2-609, Nogecho, Naka-ku, Yokohama-ku, Kanagawa Prefecture Naoki, Konan, Kanagawa 1-17-1-402 (72) Inventor Eiji Ando 553-3-205 F-term (reference) 4F072 AA02 AB02 AB04 AB05 AD47 AE08 AF02 AH06 AK05 AL11 4J002 AA01Y BB02Y BB11Y BD144 BD15Y BG104 BQ004 CF00Y CH054 CP05X CP06X CP09X CP17W CP17X CP18W CP18X CP19W CQ014 DD036 DD056 DD066 DD086 DE186 DE196 DF036 DG036 DG046 DH046 EG016 FA114Y FD01Y FD114 FD116 G01A02 GB01 GA01 A02GA00 GA01A02A FF17 FF18 FF20 FF21 GG01 HH00 5H029 AJ01 AK03 AL12 AM03 AM04 AM05 AM07 AM16 EJ12 HJ02

Claims (17)

[Claims] (1) Formula (A): Wherein R ¹ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms;
² independently of each other, an alkylene group having 1 to 18 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, an arylalkylene group having 7 to 21 carbon atoms, a dialkyl (poly) silylene group, a diaryl ( A poly) silylene group, or a direct bond, and Z ¹ is a polyoxyalkylene, (poly) carbonate, (poly) ester,
It represents a divalent group derived from polyacrylate, polymethacrylate, or alkylene, or a direct bond. And a compound represented by the formula (B): [In the formula, R ³ is independently a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. And n ¹ represents an integer of 0 to 500. ]
A linear copolymer obtained by an addition reaction with a compound represented by the formula (I) and having two terminal hydrosilyl groups, a compound represented by the formula (A) and / or a compound represented by the formula (B) Formula (D) having three or more alkenyl groups in the presence or absence of a compound represented by the following formula: [Wherein, R ⁴ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms;
⁵ is independently a heteroatom-containing alkylene group having 1 to 50 heteroatoms and 13 to 400 carbon atoms, (poly)
Carbonate, (poly) ester, polyacrylate,
Or a divalent group derived from polymethacrylate, n ² is an integer of 3 or more, and Z ² is a linking group having the same valence as n ^2, and is a carbon atom, a silicon atom, A substituted trivalent silicon atom, an aliphatic group having 1 to 30 carbon atoms, an organic group having 1 to 6 hetero atoms and containing a hetero atom having 1 to 30 carbon atoms, a benzene polycarboxy group, a phosphate group, and 2 to 50 silicon atoms Represents a linear, branched or cyclic alkylpolysiloxane group or an alkylarylpolysiloxane group. ] A gel composition comprising a polymer obtained by subjecting the compound represented by the above to an addition reaction, and a solvent. 2. The composition according to claim 1, wherein the compound represented by the formula (D) is reacted in the absence of the compound represented by the formula (A) and the compound represented by the formula (B). 3. The composition according to claim 1, wherein the compound represented by the formula (D) is reacted in the presence of the compound represented by the formula (A). 4. The composition according to claim 1, wherein the compound represented by the formula (D) is reacted in the presence of the compound represented by the formula (B). 5. The composition according to claim 1, wherein the compound represented by the formula (D) is reacted in the presence of the compound represented by the formula (A) and the compound represented by the formula (B). 6. The composition of claim 1, wherein Z ¹ is a divalent chain derived from a polyoxyalkylene, (poly) carbonate, (poly) ester, polyacrylate, polymethacrylate, or alkylene. 7. A compound of the formula (A): (Wherein R ¹ , R ² and Z ¹ are as defined in claim 1), a compound represented by the formula (B): (Wherein R ³ and n ¹ are as defined in claim 1), and a compound represented by the formula (D): (Wherein R ⁴ , R ⁵ , n ² , and Z ² are as defined in claim 1), and a polymer obtained by simultaneously performing an addition reaction of the compounds represented by the following formulas, and a solvent. Gel composition. 8. The composition of claim 7, wherein Z ¹ is a divalent chain derived from a polyoxyalkylene, (poly) carbonate, (poly) ester, polyacrylate, polymethacrylate, or alkylene. 9. Formula (B): [In the formula, R ³ is independently a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. And n ¹ represents an integer of 0 to 500. ]
And a compound represented by the formula (D) having three or more alkenyl groups: [Wherein, R ⁴ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms;
⁵ is independently a heteroatom-containing alkylene group having 1 to 50 heteroatoms and 13 to 100 carbon atoms, (poly)
Carbonate, (poly) ester, polyacrylate,
Or a divalent group derived from polymethacrylate, n ² is an integer of 3 or more, and Z ² is a linking group having the same valence as n ^2, and is a carbon atom, a silicon atom, A substituted trivalent silicon atom, an aliphatic group having 1 to 30 carbon atoms, an organic group having 1 to 6 hetero atoms and containing a hetero atom having 1 to 30 carbon atoms, a benzene polycarboxy group, a phosphate group, and 2 to 50 silicon atoms Represents a linear, branched or cyclic alkylpolysiloxane group or an alkylarylpolysiloxane group. A gel composition comprising a polymer obtained by subjecting a compound represented by the formula (1) to a hydrosilylation reaction, and a solvent. 10. The composition according to claim 1, wherein the content of the solvent is 50 to 99% by weight. 11. A gel ion conductive composition comprising the composition according to claim 1 and an electrolyte. 12. The electrolyte according to claim 1, wherein the electrolyte is an electrolyte.
12. The composition according to claim 11, which is already present in producing the composition according to claim. 13. The composition according to claim 11, which has a storage modulus of 3000 Pascal or more. 14. Its viscosity at 40 ° C. is 10,000
14. The composition according to any one of claims 11 to 13, further comprising a modified silicone having a cP or less. 15. The method according to claim 1, wherein the ionic conductivity at −20 ° C. is 50% or more of the electrolytic solution comprising the electrolyte and the solvent.
15. The composition according to any one of 1 to 14. 16. The method according to claim 11, further comprising a particulate, fibrous, or porous film-shaped thermoplastic resin.
A composition according to any one of the preceding claims. 17. A battery comprising the gelled ion conductive composition according to claim 11. Description: